WO2018135666A1

WO2018135666A1 - Spout

Info

Publication number: WO2018135666A1
Application number: PCT/JP2018/001957
Authority: WO
Inventors: 丈太郎長尾; 耕太岡本; 岩崎　力; 正毅青谷; 諭男木村
Original assignee: 東洋製罐グループホールディングス株式会社
Priority date: 2017-01-23
Filing date: 2018-01-23
Publication date: 2018-07-26
Also published as: JP2018118747A; JP6870342B2

Abstract

At least a part of the periphery of an opening (102a, 210a), through which a content liquid in a spout (101, 210) is spouted, is formed by a liquid-repellent member (122, 211) by attaching the liquid-repellent member (122, 211) to at least a part of the periphery of the opening (102a, 210a), and hence liquid repellency can be easily provided to the periphery of the opening (102a, 210a) through which the content liquid is spouted.

Description

Pouring tool

The present invention relates to a pouring tool.

Conventionally, in a pouring container for storing seasonings such as soy sauce, sauce, dressing, etc., the device has been devised to improve the drainage when pouring out the content liquid and prevent dripping. For example, it is known to form a spout lip that is expanded outward and curved on the periphery of the upper end of an inner stopper attached to the mouth of a container body as a pouring tool (see, for example, Patent Document 1).

In recent years, various techniques using liquid repellency due to a fine uneven structure have been proposed. For example, in Patent Document 2, a thin layer made of a low surface energy substance having water repellency is laminated on the surface of a fine first concavo-convex shape on the order of several tens of microns to contain fine particles (colloidal silica). By forming the second concavo-convex shape having a surface roughness smaller than the first concavo-convex shape on the surface of the layer, it is possible to achieve super water repellency with a contact angle with water of 150 degrees or more. (See [0021] of Patent Document 2).

Also, as a technique for imparting liquid repellency by increasing the contact angle of droplets, it is also known to attach hydrophobic oxide fine particles to the surface in contact with the contents. For example, according to Patent Document 3, it is said that the contact angle of pure water shows 150 degrees or more by attaching hydrophobic oxide fine particles to the outermost surface of the packaging material (see [0051] of Patent Document 3). ).

JP 2000-203619 A JP 2003-1736 A JP 2010-184454 A

By the way, in the case where a spout lip portion that is expanded outward and curved is formed on the upper end periphery of the inner plug as in the spout container of Patent Document 1, the liquid breakage is reduced during use. However, dripping may occur. And, since a part of the dripping content liquid adheres to the inner plug or cap and solidifies, it impairs cleanliness and makes the user uncomfortable. Therefore, establishment of technology for preventing dripping has been demanded. .

Therefore, the present inventors apply a technique for increasing liquid contact repellency by increasing the contact angle of the liquid droplets as disclosed in Patent Documents 2 and 3, thereby improving the falling property of the liquid droplets. Therefore, intensive studies have been made to provide a pouring tool with excellent liquid drainage.

However, when the processing for imparting liquid repellency is directly applied to the pouring tool such as the inner stopper provided in the pouring container of Patent Document 1, the handling is complicated and the processing is performed with high productivity. It came to the knowledge that there was a limit in applying.
In addition, as in the techniques disclosed in Patent Documents 2 and 3, when trying to impart liquid repellency using fine particles, the problem of contamination by foreign matters due to the removal of such fine particles is easily recalled.

The present invention has been made in view of the circumstances as described above, and an object thereof is to provide a pouring tool that can easily provide liquid repellency around the opening from which the content liquid is poured. And

In the pouring tool according to the present invention, a liquid repellent member is attached to at least a part of the periphery of the opening from which the content liquid is poured, and at least a part of the periphery of the opening is formed by the liquid repellent member. It is as a configuration.

According to the present invention, the liquid repellent member is attached around the opening from which the content liquid is poured, and at least a part of the periphery of the opening is formed by the liquid repellent member. Liquidity can be imparted.

It is a half sectional view of the extraction tool which concerns on 1st embodiment of this invention. In 1st embodiment of this invention, it is explanatory drawing which shows typically an example of the rough surface formed in the surface of a liquid repellent member. FIG. 3 is an explanatory diagram schematically showing a contact pattern of droplets on the surface of the liquid repellent member shown in FIG. 2 using a Cassie-Baxter model and a Wenzel model. In 1st embodiment of this invention, it is explanatory drawing which shows typically the other example of the rough surface formed in the surface of a liquid repellent member. It is explanatory drawing which shows the structure of the metal mold | die principal part which shape | molds the part enclosed with a dashed line in FIG. It is explanatory drawing which shows the state which poured the content liquid by inclining the extraction tool which concerns on 1st embodiment of this invention. It is explanatory drawing which shows the modification of the extraction tool which concerns on 1st embodiment of this invention. It is explanatory drawing which shows the example which applied the extraction tool which concerns on 2nd embodiment of this invention to the droplet lower nozzle of the eye drop container, (a) is sectional drawing of the whole eye drop container, (b) is (a). It is an expanded sectional view of the tip portion of the nozzle shown. In 2nd embodiment of this invention, it is explanatory drawing which shows typically the form of the rough surface formed in the surface of a liquid repellent member. FIG. 10 is an explanatory diagram schematically showing a contact pattern of droplets on the surface of the liquid repellent member shown in FIG. 9 using a Cassie-Baxter model and a Wenzel model. It is explanatory drawing which shows typically the state of the droplet in an example of the nozzle under a droplet which concerns on embodiment of this invention. It is explanatory drawing which shows the dispersion | variation in dripping amount typically. It is explanatory drawing which shows the other example which applied the extraction tool which concerns on 2nd embodiment of this invention to the droplet lower nozzle of the eye drop container, (a) is sectional drawing of the whole eye drop container, (b) is (a It is an expanded sectional view of the tip portion of the nozzle shown in FIG. It is explanatory drawing which shows typically the state of the droplet in the other example which applied the extraction tool which concerns on 2nd embodiment of this invention to the droplet lower nozzle of the eye drop container.

Hereinafter, an embodiment of a dispensing tool according to the present invention will be described with reference to the drawings.

[First embodiment]
First, a first embodiment of the dispensing tool according to the present invention will be described.

[Pouring tool]
The pouring tool 101 shown in FIG. 1 includes an inner tube portion 103 and an outer tube portion 104 that hang concentrically with a spout portion 102 that serves as a spout for the content liquid stored in a container body (not shown). Used as an inner plug at the mouth of the container body.
FIG. 1 is a half sectional view combining a front view and a longitudinal sectional view of the dispensing tool according to the present embodiment.

When the pouring tool 101 is attached to the mouth portion of the container body, the inner cylindrical portion 103 is in close contact with the inner peripheral surface of the mouth portion of the container body. At the same time, the annular fitting portion 140 formed along the circumferential direction on the inner peripheral surface on the lower end side of the outer cylindrical portion 104 is fitted with the fitting portion formed on the outer peripheral surface side of the mouth portion of the container body. It is designed to be liquid-tightly attached to the mouth of the container body by a stopper. Furthermore, the extraction tool 101 is provided with an annular protrusion 110 that comes into contact with the top surface of the mouth of the container body so that the extraction tool 101 can be attached to the mouth of the container body in a more liquid-tight manner.

Further, the spout part 102 has a cylindrical main part 121 that rises in a cylindrical shape, and an opening part 102a through which the content liquid is poured out is provided on the inner peripheral side thereof. And the sealing partition 120 is provided in the inner peripheral side of the base part, and it can open now by tearing the sealing partition 120 from the notch (score) 120a formed cyclically | annularly along the circumferential direction. Yes. After opening, the content liquid stored in the container body is poured out through the spout portion 102 by tilting the container body (see FIG. 6).

In the present embodiment, the pouring tool 101 that is used as an inner plug attached to the mouth portion of the container main body is the periphery of the opening portion 102 a provided in the pouring port portion 102, that is, the top surface side of the pouring port portion 102. The portion is formed by a liquid repellent member 122 to which liquid repellency is imparted.

[Liquid repellent material]
In the present embodiment, the liquid repellent member 122 is made of a non-fluorine resin, and fluorine atoms are incorporated in the molecular chain of the non-fluorine resin that forms the surface of the liquid repellent member 122. For example, when a molecular chain of a non-fluorine resin is represented by — (CH ₂ ) n—, a fluorine atom is incorporated into a part of the molecular chain, and a fluorine-containing moiety such as —CHF— or —CF ₂ — is generated. Thus, the surface of the liquid repellent member 122 is fluorinated.

Incorporation into the molecular chain of the non-fluorine resin forming the surface of the liquid repellent member 122 can be performed by etching using fluorine plasma. For example, CF ₄ gas, SiF ₄ gas, or the like is used, the surface of the liquid repellent member 122 (the base material on which the liquid repellent member 122 before fluorination is formed) is disposed between a pair of electrodes, and a high frequency electric field is applied. Thus, fluorine atom plasma (atomic fluorine) is generated and collided with the surface of the liquid repellent member 122, so that the fluorine atoms are molecules of the non-fluorine resin forming the surface of the liquid repellent member 122. Incorporated into the chain. That is, the resin on the surface is vaporized or decomposed, and at the same time, fluorine atoms are incorporated.
Accordingly, ultra fine irregularities are formed by etching in the region where fluorine atoms are incorporated. The arithmetic average roughness Ra of the ultra-fine irregularities is generally 100 nm or less and Ra / RSm ≧ 5 × 10 ⁻³ .

Further, the surface of the liquid repellent member 122 can be roughened so that a fine uneven shape is formed as required (see FIG. 2). For example, a stamper on which a rough surface corresponding to a desired uneven shape is formed by a resist method or the like is heated to an appropriate temperature, and this is pressed against the surface of the liquid repellent member 122 to transfer the rough surface. The surface of the member 122 can be roughened.

In roughening the surface of the liquid repellent member 122, an auxiliary uneven shape sRS smaller than the uneven shape may be formed on at least a part of the surface of the fine uneven shape (see FIG. 4). . For example, if a finer concavo-convex shape is formed on a stamper in which a fine concavo-convex shape is formed by blasting or the like and transferred, the surface structure of the liquid repellent member 122 is relatively large. The surface of the liquid repellent member 122 can be roughened so as to have an uneven shape and a relatively small auxiliary uneven shape sRS formed on the surface.

The non-fluorine resin used for the liquid repellent member 122, that is, a resin not containing fluorine, can be roughened by forming an uneven shape on the surface of the liquid repellent member 122, and fluorine atoms can be removed by fluorine plasma etching. Any thermoplastic resin, thermosetting resin, photocurable resin, and the like can be used as long as the incorporation into the molecular chain is possible. For example, polyethylene, polypropylene, ethylene, or an olefin resin typified by a copolymer of propylene and another olefin, or a polyester such as polyethylene terephthalate (PET), polyethylene isophthalate, or polyethylene naphthalate is preferably used.

[Operation principle of liquid repellent member]
Hereinafter, the operation principle of the liquid repellent member 122 in the present embodiment will be described with reference to FIGS.
FIG. 2 shows an example of a rough surface formed on the surface of the liquid repellent member 122 in the present embodiment. In the figure, the surface of the liquid repellent member 122 is formed with a rough surface RS having a fine concavo-convex shape (in FIG. 2, the top of the convex portion in the rough surface RS is indicated by S). Fluorine atoms are incorporated in the molecular chain of the non-fluorine resin forming the rough surface RS.

The liquid repellency of the droplet Du on the rough surface RS will be described with reference to FIG.
As shown in FIG. 3A, the contact pattern of the droplet Du on the rough surface RS as described above is such that the concave portion in the rough surface RS is air in the Cassie mode in which the droplet Du is placed on the rough surface RS. It is a pocket, and the droplet Du is in a composite contact state between the solid and the gas (air). In such a composite contact, the contact radius R at the contact interface of the droplet Du is small, the adhesion between the droplet Du and the rough surface is low, and the liquid comes into contact with the air having the highest lyophobic property. Sex is expressed. The contact angle of the rough surface RS in the Cassie mode is as shown in the following theoretical formula (1).
^{_{cosθ * = (1-φ S}} ) cosπ + φ S cosθ E
= Φ _S -1 + φ _S cosθ _E (1)
θ _E : contact angle θ ^* : apparent contact angle φ _S : area ratio (projected area of solid-liquid interface per unit area)
As can be understood from the theoretical formula (1), the smaller the φ _S , the closer the apparent contact angle θ ^* approaches 180 degrees and the super liquid repellency is exhibited.

On the other hand, as shown in FIG. 3B, when the droplet Du enters the concave portion in the rough surface RS, the droplet Du is not in contact with the composite as described above, but in contact with only the solid. Shown in mode. In such a Wenzel mode, the contact radius R at the contact interface of the droplet Du is large, and the adhesion between the droplet Du and the rough surface is high. The contact angle of the uneven surface is as shown in the following theoretical formula (2).
cosθ ^* = rcosθ _E (2)
θ _E : Contact angle θ ^* : Apparent contact angle r: Concavity and convexity (= actual contact area / droplet projection area)
As understood from the theoretical formula (2), as r is larger, the apparent contact angle θ ^* approaches 180 degrees and exhibits super-liquid repellency.

Here, with regard to the liquid repellency, as described above, it is known that the liquid repellency is improved in both the Wenzel mode and the Cassie mode, but the adhesion between the rough surface RS and the droplet Du is improved. In order to reduce and improve the falling property for the droplet Du, it is considered necessary to stably maintain the Cassie mode, not the Wenzel mode, that is, to stably maintain the air pockets of the recesses.
That is, in the Wenzel mode, the interface between the liquid phase and the solid phase is large, and as a result, the physical adsorption force acting on the interface also increases, so that the contact angle is large and the liquid repellent, but the droplet Du falls easily. do not do.
On the other hand, in the Cassie mode, since the interface is small, the adhesion force that must be overcome when the droplets Du fall is low, and the droplets can easily fall and repeatedly fall over again.

Therefore, in the present embodiment, in order to effectively maintain the contact of the droplet Du in the Cassie mode, fluorine is contained in the molecular chain of the non-fluorine resin forming the rough surface RS of the liquid repellent member 122. By incorporating atoms, liquid repellency is imparted chemically.
That is, if the liquid enters the concave portion in the rough surface RS, the contact pattern of the droplet Du becomes the Wenzel mode. As a result, the super-liquid repellency by the Cassie mode is impaired. In the embodiment, by incorporating fluorine atoms into the molecular chain of the non-fluorine resin that forms the rough surface RS, the liquid repellency can be chemically imparted to the rough surface RS, and thereby into the recess. The penetration of the liquid is effectively suppressed, and the super liquid repellency by the Cassie mode is stably maintained.

In particular, in this embodiment, at least a part of the rough surface RS, for example, at the top of the convex portion or the bottom of the concave portion, the chemical liquid repellency is expressed in the molecular chain of the non-fluorine resin forming this surface. The fluorine atom is incorporated. For this reason, even when the liquid repeatedly contacts the rough surface RS, the fluorine atoms are not removed and the chemical liquid repellency is stably maintained. As a result, the super liquid repellency by the Cassie mode is maintained. Without being lowered, the high level is maintained as in the initial stage.
Furthermore, since a fluorine atom is incorporated into the molecular chain of the non-fluorine resin on the surface instead of forming a film containing fluorine atoms, there is no problem of contamination due to peeling or dropping.

Here, the degree of the concavo-convex shape of the rough surface RS is expressed by the area of the convex top S per unit area in the rough surface RS so that the liquid repellency by the Cassie mode is sufficiently exhibited. It is preferable that the area ratio φs is in the range of 0.05 or more, preferably 0.08 or more.
Further, from the viewpoint of moldability and mechanical strength, the area ratio φs is preferably 0.8 or less, particularly preferably 0.5 or less.
The depth d in the rough surface RS is preferably in the range of 5 to 200 μm, particularly 10 to 50 μm.

In the present embodiment, the rough surface formed on the surface of the liquid repellent member 122 is not limited to the uneven shape of the rough surface RS shown in FIG. 2, but from the viewpoint of stably forming the air pocket, FIG. It is preferable that the convex part and the concave part as shown are formed in a rectangular shape. For example, if the recess has a V-shaped form, the droplet Du can easily enter the recess.
Further, in order to more effectively suppress the intrusion of the liquid droplet Du into the concave-convex concave portion of the rough surface RS, as shown in FIG. It is preferable to form an auxiliary uneven shape sRS smaller than the uneven shape. In this way, when the droplet Du is placed on the rough surface RS, an air pocket is also formed between the droplet Du and the auxiliary concave / convex shape sRS. Intrusion of the droplet Du into the concave and convex portions is prevented, and the super-liquid repellency by the Cassie mode is more stably maintained.

The surface of the liquid repellent member 122 is preferably fluorinated and roughened in order to improve the liquid repellency. However, if the surface of the liquid repellent member 122 is at least fluorinated, the surface is repellent. Liquid performance can be demonstrated. In addition, as described above, the plasma treatment for fluorinating the surface of the liquid repellent member 122 is very strong in attack, and fine irregularities are formed on the surface of the liquid repellent member 122 by the plasma treatment. Roughened.
Therefore, the surface of the liquid repellent member 122 only needs to be at least fluorinated, and may be any surface that further roughens the surface of the liquid repellent member 122 as necessary.

[Structure of spout part]
In the example shown in FIG. 1, an annular liquid repellent member 122 having an overhanging portion 122 a that protrudes outward with respect to the outer peripheral surface of the cylindrical main portion 121 is formed in a cylindrical shape at the spout portion 102 of the extraction tool 101. It is attached to the opening edge of the cylindrical main part 121 that rises. The inner diameter of the liquid repellent member 122 formed in an annular shape is the same as the inner diameter of the cylindrical main portion 121 so that the inner peripheral surface of the liquid repellent member 122 is flush with the inner peripheral surface of the cylindrical main portion 121. It is the diameter. Thereby, the site | part of the top | upper surface side of the spout part 102 is comprised by the liquid repellent member 122 over the perimeter.
Further, on the inner peripheral surface side of the liquid repellent member 122, the opening side edge portion of the cylindrical main portion 121 is cut out along the circumferential direction, and the opening side edge portion of the cylindrical main portion 121 is cut. An engagement step portion 122b is formed to be engaged with the liquid repellent member 122 so that the liquid repellent member 122 is joined in an engaged state with the opening side edge portion of the cylindrical main portion 121 at a portion excluding the overhang portion 122a. I have to.

In order to attach the liquid repellent member 122 to the spout portion 102 of the dispensing tool 101, it may be attached by appropriate means such as ultrasonic fusion, thermal fusion, adhesive, fitting, etc., or may be removable.
Further, for example, as shown in FIG. 5, the liquid repellent member 122 may be disposed as an insert material in a mold and attached by molding the extraction tool 101 by in-mold molding.
5 shows the structure of the main part of the mold for molding the portion surrounded by the chain line in FIG. 1 when the liquid repellent member 122 is placed in the mold as an insert material and the pouring tool 101 is molded in-mold. It is explanatory drawing shown.

In in-mold molding, when the liquid repellent member 122 is pressed against the cavity surface by the molten resin injected into the mold in a pressurized state, the uneven shape of the rough surface RS of the liquid repellent member 122 is crushed and repelled. Although there is a concern that the liquidity is impaired, such a problem can be effectively avoided by making the structure of the spout portion 102 as shown in FIG.
That is, the flow direction of the resin that forms the cylindrical main portion 121 during in-mold molding is indicated by an arrow in FIG. 5, and has a protruding portion 122 a that protrudes outward with respect to the outer peripheral surface of the cylindrical main portion 121. The liquid repellent member 122 is joined to the opening side edge of the cylindrical main part 121 by joining the liquid repellent member 122 to the opening side edge of the cylindrical main part 121 at a portion other than the overhanging part 122a. Although the injection resin pressure is applied to the inner peripheral surface side portion (engagement step portion 122b) of the liquid repellent member 122, it is possible to prevent the injection resin pressure from being applied to the overhang portion 122a. Thereby, it is possible to prevent the uneven shape of the rough surface RS of the liquid repellent member 122 from being crushed at least in the overhanging portion 122a, so that the liquid repellency is not impaired.

Since the liquid repellent member 122 is a member smaller than the pouring tool 101, the transport efficiency during fluorination / roughening can be improved, the processing apparatus can be downsized, and the number that can be fluorinated / roughened simultaneously. It can also be increased. Alternatively, the lyophobic member 122 can be produced by punching a film-like or sheet-like base material and then punching it.
Therefore, by attaching the liquid repellent member 122 to the spout portion 102 so that the top surface side portion of the spout portion 102 is formed by the liquid repellent member 122, the spout serving as the spout for the content liquid is formed. Liquid repellency can be easily imparted to the portion 102. Then, as shown in FIG. 6 (a), when a necessary amount of the content liquid is poured through the outlet portion 102 of the tilted dispensing tool 101, the droplets are poured as shown in FIG. 6 (b). By falling from the top surface of the outlet portion 102, it is possible to exhibit excellent liquidity.

As described above, the present invention has been described with reference to the first embodiment. However, according to this embodiment, a liquid repellent member is attached to the spout portion, and at least a part of the top surface side of the spout portion is a liquid repellent member. Thus, it is possible to easily impart liquid repellency to the spout portion and to exhibit excellent liquid drainage.
Such a pouring tool according to the first embodiment of the present invention uses, for example, soy sauce, sauces, dressings and other seasonings, detergents, cosmetics and other chemicals as the content liquid, and pours such content liquid with good liquidity. Although it can utilize as a pouring tool which can be taken out, it is not limited only to embodiment mentioned above, and it cannot be overemphasized that various change implementation is possible in the scope of the present invention.

For example, in the above-described embodiment, the engagement step portion 122b formed by cutting out the thickness of the opening side edge portion of the cylindrical main portion 121 is formed on the inner peripheral surface side of the liquid repellent member 122. The liquid member 122 is joined in a state where the liquid member 122 is engaged with the opening-side edge portion of the cylindrical main portion 121 at a portion other than the overhang portion 122a, but is not limited thereto. As shown in FIG. 7, the liquid repellent member 122 may be joined to the opening side edge of the cylindrical main portion 121.

In the modification shown in FIG. 7, the opening-side edge portion of the cylindrical main portion 121 is notched obliquely along the circumferential direction, and is formed in a tapered shape that is inclined downward toward the outer peripheral surface side. In addition, a tapered curved surface portion 122 c that abuts on the opening side edge of the cylindrical main portion 121 is formed on the inner peripheral surface side of the liquid repellent member 122. As a result, the liquid repellent member 122 is joined in a state where the liquid repellent member 122 is in contact with the opening side edge of the cylindrical main portion 121 at a portion other than the overhang portion 122a.
Here, FIG. 7A is a one-side cross-sectional view of the present modified example, and in this modified example, the liquid repellent member 122 is placed in a mold as an insert material, and the pouring tool 101 is in-mold molded. FIG. 7B shows the structure of the main part of the mold for molding the portion surrounded by the chain line in FIG.

In FIG. 7B, the resin pressure P applied to the tapered curved surface portion 122c of the liquid repellent member 122 and its component force during in-mold molding are indicated by arrows, and the opening side of the cylindrical main portion 121 formed in a tapered shape. Although the gradient of the edge portion is indicated by θ, the force to press the liquid repellent member 122 against the cavity surface is attenuated to P · cos θ.
Therefore, according to this modification, although the injection resin pressure is applied to the inner peripheral surface side portion (tapered curved surface portion 122c) of the liquid repellent member 122 joined to the opening side edge of the cylindrical main portion 121, The force that tries to press the part against the cavity surface can be attenuated. As a result, it is possible to suppress the concavo-convex shape of the rough surface RS of the liquid repellent member 122 from being crushed even in the portion excluding the overhanging portion 122a. Can be kept intact.

In the above-described embodiment, the top surface side portion of the spout portion 102 is formed by the annular liquid repellent member 122 over the entire circumference, but the present invention is not limited to this. For example, although not particularly illustrated, the pouring tool 101 has a form in which a lid for sealing the pouring part 102 is connected via a hinge part. The content liquid is poured out from the side opposite to the side to which the lid is connected. When the present invention is applied to the pouring tool 101 having such a configuration, the liquid repellent member 122 is attached to a portion through which at least the content liquid of the spout portion 102 passes and including the top surface thereof. At least a part of the top surface side of the spout portion 102 can be formed by the liquid repellent member 122.
Moreover, although the spout part 102 has the cylindrical main part 121 which stands | starts up cylindrically like the embodiment mentioned above, the cylindrical main part 121 is formed in a rectangular tube shape as needed. You may form so that it may stand up.

[Second Embodiment]
Next, the second embodiment of the pouring tool according to the present invention will be described. However, the pouring tool according to the present embodiment can be suitably used as a nozzle of various containers or apparatuses, and liquid can be dripped little by little. It is what.

In general, an eye drop container or the like is provided with a nozzle at a dispensing portion so that a liquid (eye drop) in the container can be dropped little by little.
Here, the human eye usually has a volume for holding about 20 μL of tear fluid, but with a conventional eye dropper nozzle, the drop volume of one drop is generally about 30-40 μL. There was a problem that almost half of the dropped eye drops overflowed from the eyes.
In view of this, a proposal has been made regarding a nozzle for an eye drop container that allows a smaller amount of dripping corresponding to the tear volume of human eyes.

For example, in International Publication No. 2014/123140, a drop of one drop is provided by providing a needle portion having an outer diameter of 0.5 mm or more and 2.5 mm or less at the tip of a dispensing nozzle for dropping an ophthalmic solution from a container. An “eye drop container” has been proposed that can have an amount of about 5 to 25 μL.

However, in the “eye drop container” described in International Publication No. 2014/123140, the amount of dripping is intended to be reduced by providing a fine needle part at the tip of the nozzle, but the nodule part itself is repellent. There was no liquid performance, and during the dropping, there was a problem that the liquid droplet adhered or remained on the tip of the nozzle including the needle portion, and as a result of repeated use, the quantitative dropping could not be performed.
In addition, a fine needle of 0.5 to 2.5 mm has a fear that it may be pierced into the eye because the tip of the needle looks very sharp for a user who is instilling.
Even with such a fine needle, the amount of dripping is limited to about 10 μL at most, and it cannot be said that the amount of dripping is small enough.

Hereinafter, the example which applied the extraction tool which concerns on this embodiment to the nozzle under a droplet of the container for eye drops is demonstrated.
FIG. 8 is an explanatory view showing an example in which the dispensing tool according to the present embodiment is applied to a lower droplet nozzle of an eye drop container, (a) is a sectional view of the whole eye drop container, and (b) is a view (a). It is an expanded sectional view of the tip portion of the nozzle shown.

[Eye container]
As shown in the figure, the droplet lowering nozzle to which the dispensing tool according to the present embodiment is applied constitutes a nozzle 210 serving as a spout for an eye drop container 201 for eye drops.
Specifically, the eye drop container 201 includes a container main body 202 that can store and store a liquid serving as an eye drop therein, and a liquid that protrudes from substantially the center of the upper surface of the container main body 202 (the bottom surface when using the drop). A nozzle 210 serving as a spout is provided. The container main body 202 and the nozzle 210 communicate with each other, and the eye drops stored in the container main body 202 are poured out and dripped from the opening 210a of the nozzle 210 to the outside of the container.

A cap (not shown) is detachably attached to the container body 202 including the nozzle 210. The nozzle 210 is covered with the cap, the inside of the container body 202 is sealed, and the nozzle 210 is sealed. The tip of can be protected.

[nozzle]
As shown in FIG. 8, the nozzle 210 is formed separately from the container main body 202, and is inserted and fitted into a nozzle mounting protrusion formed at the mouth of the container main body 202, so that the container main body 202 is inserted. And the eye drop container 201 are formed.
Specifically, the nozzle 210 is formed in a cylindrical shape or a rectangular tube shape, for example, and communicates with the liquid storage space of the container body 202. Then, liquid is poured out and dropped from the inside of the container body 202 through the opening 210 a of the cylindrical nozzle 210.

In the present embodiment, the liquid repellent member 211 is attached to the front end side where the opening 210 a of the nozzle 210 opens, and the liquid repellent member 211 constitutes at least a part of the front end of the nozzle 210. ing.

[Liquid repellent material]
In the present embodiment, the liquid repellent member 211 is made of a non-fluorine resin, and fluorine atoms are incorporated in the molecular chain of the non-fluorine resin that forms the surface of the liquid repellent member 211. For example, when a molecular chain of a non-fluorine resin is represented by — (CH ₂ ) n—, a fluorine atom is incorporated into a part of the molecular chain, and a fluorine-containing moiety such as —CHF— or —CF ₂ — is generated. Thus, the surface of the liquid repellent member 211 is fluorinated.

Incorporation into the molecular chain of the non-fluorine resin forming the surface of the liquid repellent member 211 can be performed by etching using fluorine plasma. For example, CF ₄ gas, SiF ₄ gas, or the like is used, and the surface of the liquid repellent member 211 (a substrate on which the liquid repellent member 211 before fluorination is formed) is disposed between a pair of electrodes, and a high frequency electric field is applied. Thus, fluorine atom plasma (atomic fluorine) is generated and collided with the surface of the liquid repellent member 211, so that the fluorine atoms are molecular chains of the non-fluorine resin forming the surface of the liquid repellent member 211. Built in. That is, the resin on the surface is vaporized or decomposed, and at the same time, fluorine atoms are incorporated.
Accordingly, ultra fine irregularities are formed by etching in the region where fluorine atoms are incorporated. The arithmetic average roughness Ra of the ultra-fine irregularities is generally 100 nm or less and Ra / RSm ≧ 5 × 10 ⁻³ .

Further, the surface of the liquid repellent member 211 can be roughened so that fine irregularities are formed as necessary. For example, a liquid repellent member is formed by heating a stamper on which a rough surface portion corresponding to desired unevenness by a resist method or the like is heated to an appropriate temperature, and pressing this against the surface of the liquid repellent member 211 to transfer the rough surface portion. The surface of 211 can be roughened.

As the non-fluorine-based resin used for the liquid repellent member 211, that is, a resin not containing fluorine, an uneven portion can be formed on the surface of the liquid repellent member 211 to be roughened, and fluorine atoms can be removed by fluorine plasma etching. Any thermoplastic resin, thermosetting resin, photocurable resin, and the like can be used as long as the incorporation into the molecular chain is possible. For example, polyethylene, polypropylene, ethylene, or an olefin resin typified by a copolymer of propylene and another olefin, or a polyester such as polyethylene terephthalate (PET), polyethylene isophthalate, or polyethylene naphthalate is preferably used.

[Operation principle of liquid repellent member]
Hereinafter, the operation principle of the liquid repellent member 211 in the present embodiment will be described with reference to FIGS. 9 and 10.
In this embodiment, the form of the rough surface formed on the surface of the liquid repellent member 211 is shown in FIG. In the figure, the surface of the liquid repellent member 211 is formed with a rough surface RS composed of fine irregularities (in FIG. 9, the top of the convex portion in the rough surface RS is indicated by S), Fluorine atoms are incorporated in the molecular chain of the non-fluorinated resin that forms the rough surface RS.

The liquid repellency of the liquid on the rough surface RS will be described with reference to FIG.
As shown in FIG. 10 (a), the contact pattern of the droplet Du on the rough surface RS as described above is such that in the Cassie mode in which the droplet Du is placed on the rough surface RS, the recesses in the rough surface RS are air. It is a pocket, and the droplet Du is in a composite contact state between the solid and the gas (air). In such a composite contact, the contact radius R at the contact interface of the droplet Du is small, the adhesion between the droplet Du and the rough surface is low, and the liquid comes into contact with the air having the highest lyophobic property. Sex is expressed. The contact angle of the rough surface RS in the Cassie mode is as shown in the following theoretical formula (1).
^{_{cosθ * = (1-φ S}} ) cosπ + φ S cosθ E
= Φ _S -1 + φ _S cosθ _E (1)
θ _E : contact angle θ ^* : apparent contact angle φ _S : area ratio (projected area of solid-liquid interface per unit area)
As can be understood from the theoretical formula (1), the smaller the φ _S , the closer the apparent contact angle θ ^* approaches 180 degrees and the super liquid repellency is exhibited.

On the other hand, as shown in FIG. 10B, when the liquid droplet Du enters the concave portion in the rough surface RS, the liquid droplet Du is not in contact with the composite as described above, but in contact with only the solid. Shown in mode. In such a Wenzel mode, the contact radius R at the contact interface of the droplet Du is large, and the adhesion between the droplet Du and the rough surface is high. The contact angle of the uneven surface is as shown in the following theoretical formula (2).
cosθ ^* = rcosθ _E (2)
θ _E : Contact angle θ ^* : Apparent contact angle r: Concavity and convexity (= actual contact area / droplet projection area)
As understood from the theoretical formula (2), as r is larger, the apparent contact angle θ ^* approaches 180 degrees and exhibits super-liquid repellency.

Here, with regard to the liquid repellency, as described above, it is known that the liquid repellency is improved in both the Wenzel mode and the Cassie mode, but the adhesion between the rough surface RS and the droplet Du is improved. In order to reduce and drop a small amount of droplets Du, it is considered necessary to stably maintain the Cassie mode, not the Wenzel mode, that is, to stably maintain the air pockets of the recesses.
That is, in the Wenzel mode, the interface between the liquid phase and the solid phase is large, and as a result, the physical adsorption force acting on the interface also increases, so that the contact angle is large and the liquid repellent, but the droplet Du easily drops.・ It will not fall.
On the other hand, in the Cassie mode, since the interface is small, the adhesion force that must be overcome when the droplet Du is dropped is low, and the droplet is easily dropped and tumbled.

Therefore, in the present embodiment, in order to effectively maintain the contact of the droplet Du in the above Cassie mode, the molecular chain of the non-fluorine resin forming the rough surface RS of the tip portion 211 of the nozzle 210 is used. Incorporation of fluorine atoms into the liquid provides chemical liquid repellency.
That is, if the liquid enters the concave portion in the rough surface RS, the contact pattern of the droplet Du becomes the Wenzel mode. As a result, the super-liquid repellency by the Cassie mode is impaired. In the embodiment, by incorporating fluorine atoms into the molecular chain of the non-fluorine resin that forms the rough surface RS, the liquid repellency can be chemically imparted to the rough surface RS, and thereby into the recess. The penetration of the liquid is effectively suppressed, and the super liquid repellency by the Cassie mode is stably maintained.

Here, the degree of unevenness of the rough surface RS as described above is represented by the area of the convex portion top S per unit area in the rough surface RS so that the liquid repellency by the Cassie mode is sufficiently exhibited. It is preferable that the area ratio φs is 0.05 or more, preferably 0.08 or more.
Furthermore, from the viewpoint of moldability and mechanical strength, the area ratio Φ is preferably in the range of 0.8 or less, particularly 0.5 or less.
The depth d in the rough surface RS is preferably in the range of 5 to 200 μm, particularly 10 to 50 μm.

In this embodiment, the rough surface formed on the surface of the liquid repellent member 211 is not limited to the uneven shape of the rough surface RS shown in FIG. 9, but from the viewpoint of stably forming the air pockets, FIG. It is preferable that the convex part and the concave part as shown are formed in a rectangular shape. For example, if the recess has a V-shaped form, the droplet Du can easily enter the recess.
Further, it is preferable that the surface of the liquid repellent member 211 is fluorinated and the surface of the tip end portion 211 is roughened in order to improve the liquid repellency, but the surface of the liquid repellent member 211 is at least If fluorinated, liquid repellency can be exhibited. In addition, as described above, the plasma treatment for fluorinating the surface of the liquid repellent member 211 is very strong in attack, and fine irregularities are formed on the surface of the liquid repellent member 211 by the plasma treatment. Roughened.
Therefore, the surface of the liquid repellent member 211 only needs to be at least fluorinated, and may be any surface that further roughens the surface of the tip portion 211 as necessary.

[Nozzle tip structure]
In the example shown in FIG. 8, a liquid repellent member 211 having an opening 211 a drilled in the same diameter and the same axis as the opening 210 a of the nozzle 210 is attached to the tip side of the nozzle 210. The tip of the nozzle 210 is configured.
In order to attach the liquid repellent member 211 to the front end side of the nozzle 210, for example, the liquid repellent member 211 may be attached by forming the nozzle 210 by in-mold molding using the insert material as an insert material, ultrasonic fusion, thermal fusion, It may be attached by appropriate means such as an adhesive or fitting, or may be removable.

Since the liquid repellent member 211 is a member smaller than the nozzle 210, the conveyance efficiency during fluorination / roughening can be improved, the processing apparatus can be downsized, and the number of fluorinated / roughening at the same time can be increased. You can also. Alternatively, the lyophobic member 211 can be manufactured by punching a film-like or sheet-like base material and then punching it.
Therefore, by attaching the liquid repellent member 211 to the tip end side of the nozzle 210 so that the tip end portion of the nozzle 210 is constituted by the liquid repellent member 211, the liquid repellency of the nozzle tip portion can be easily improved. it can.

As a result, the liquid (eye drops) poured out from the container body 202 is prevented from getting wet to the tip of the nozzle 210 over a wide range, and the liquid poured out from the nozzle 210 is adjusted and set in the inner diameter of the opening 210a. The dripping amount of can be arbitrarily set.
That is, as shown in FIG. 11, the liquid droplets Du poured out from the nozzle 210 with improved liquid repellency at the tip end are substantially spherical without spreading over the nozzle tip. Then, at the timing when the weight of the droplet Du exceeds the adhesion force between the droplet Du and the nozzle tip, the droplet Du separates from the nozzle surface and falls and drops. Since the droplets Du are not wet and spread, the adhesion is small, and the amount of droplets Du dropped is small. Moreover, by setting the inner diameter of the opening 210a of the nozzle 210 to a predetermined dimension (for example, 0.5 mm or less), a desired amount (for example, 10 μL or less) of the droplet Du can be poured out and dropped.

Moreover, even if the liquid repellency at the nozzle tip is increased, there may be variations in the amount of droplets dispensed.
FIG. 12 is an explanatory diagram schematically showing variation in the amount of dripping. As shown in FIG. 11, the droplet Du dropped from the nozzle 210 has a spherical shape at the center of the opening at the tip of the nozzle, and is detached from the tip of the nozzle when the droplet Du reaches a certain weight. Will drop and drip.

However, when the liquid repellency of the nozzle tip is uneven, the liquid droplet Du ejected from the nozzle 210 moves to a lower liquid repellency side, for example, as shown in FIG. The state is deviated from the center of the nozzle opening. In such a state, since the droplet Du becomes larger than in the normal case, the amount of the dropped droplet is also larger than in the original normal case.
Further, when the liquid is poured out from the nozzle, so-called air entrapment, in which bubbles are generated and mixed in the liquid, may occur. When such air is caught, the liquid droplet Du discharged from the nozzle 210 is separated into a plurality of liquid droplets Du having different liquid amounts as shown in FIG. 12B, for example. The droplets Du may be dropped individually or integrally, resulting in a drop amount different from the original normal case.

In order to cope with this, the tip surface of the nozzle 210 is divided into two types (two steps): a first surface located on the nozzle center side and a second surface continuous to the outer peripheral side of the first surface. As the surface configuration, the first surface and the second surface can have different surface free energies, that is, the second surface can have a higher liquid repellency than the first surface.
Here, as the liquid repellency, for example, when a target liquid (such as water) is placed on a horizontal mounting surface, a “contact angle” that is an angle formed by a tangent line between the mounting surface and the liquid surface is θ _E. In this case, if θ _E ≧ 90 °, the mounting surface is “high” (low energy surface) for the target liquid, and if θ _E <90 °, the liquid repellency The property is “low” (high energy surface).

For example, as shown in FIG. 13, a protrusion 210b that protrudes along the periphery of the opening 210a of the nozzle 210 is formed, and an opening 211a is formed with the same diameter and the same diameter as the outer diameter of the protrusion 210b. The liquid member 211 is attached to the front end side of the nozzle 210 so as to be arranged around the protrusion 210b, and the liquid repellent member 211 constitutes a part of the front end portion of the nozzle 210. (See FIG. 13B).
Thus, the tip surface of the protrusion 210b can be the first surface S1 positioned on the nozzle center side, and can be a high energy surface with low liquid repellency. Then, the surface of the liquid repellent member 211 that has been fluorinated and roughened is defined as a second surface S2 that is continuous to the outer peripheral side of the first surface, and a surface having a surface free energy lower than that of the first surface S1 (repellency). Low energy surface with high liquidity).

As a result, even if there is a variation in liquid repellency on the second surface S2, it is not affected, and even when air is caught, droplets are separated and dispersed on the second surface S2 side. As shown in FIG. 14, the liquid droplet is always guided to be formed at the center of the opening of the nozzle 210, and the liquid is surely and stably dispensed and dropped without causing any deviation or dispersion of the liquid droplet. Can be made.

When the content liquid stored in the container main body 202 is dropped, the content liquid is dropped by pressing the container main body 202 to increase its internal pressure. However, as shown in FIG. When the liquid member 211 is attached to the nozzle 210, the liquid repellent member 211 does not directly receive the internal pressure, so that the liquid repellent member 211 can be prevented from being detached due to an increase in internal pressure. Also, in order to prevent detachment more firmly, even when the liquid repellent member 211 is attached to the nozzle 210 via an adhesive, the adhesive interface and the content extraction path can be isolated, so that the adhesive Contamination can be completely prevented. Moreover, the fitting part 211 may be provided in the nozzle 210 so as to be removable, and the liquid repellent member may be replaceable. These are one of the great effects of the present invention.

As described above, the present invention has been described with reference to the second embodiment. However, according to this embodiment, a liquid repellent member is attached to the tip side of the droplet lowering nozzle, and at least the tip of the droplet lowering nozzle is formed by the liquid repellent member. By constituting a part, it is possible to easily improve the liquid repellency at the nozzle tip and to reduce the amount of dripping.
Such a dispensing tool according to the second embodiment of the present invention can be suitably used as a droplet lower nozzle of an eye drop container, but is not limited to the above-described embodiment, and the present invention. It goes without saying that various modifications can be made within the range described above.

For example, in the above-described embodiment, the eye drop container for eye drops is described as an example of the application target of the dispensing tool according to the present invention. However, the application target of the present invention is not limited to the eye drop container. That is, various liquids can be mounted on a spout part of a container or device that is desired to be dripped by a predetermined amount, and the dripping amount can be reduced. Containers for chemicals other than eye drops, soy sauce, Lubricating equipment for periodically supplying small amounts of lubricating oil to various containers such as containers for seasonings such as sauces, containers for chemical products such as detergents and cosmetics, and drive systems of machines such as chains and bearings Further, it can be used as a nozzle of various apparatuses such as a coating apparatus used for a spin coater or the like.

Further, in the above-described embodiment, the liquid repellent member whose surface is fluorinated and roughened to impart liquid repellency is used, but the liquid repellent member is not limited to this. For example, liquid repellency may be imparted by applying a liquid repellency substance such as silicone oil to the surface, or liquid repellency by attaching hydrophobic oxide fine particles such as hydrophobic silica to the surface. The thing to which the property was provided may be sufficient. Further, by forming the liquid repellent member with a fluorine-based resin such as polytetrafluoroethylene, the surface thereof can exhibit liquid repellency.

All the contents of the documents described in this specification and the content of the Japanese application that forms the basis of the Paris priority of the present application are incorporated herein.

DESCRIPTION OF SYMBOLS 101 Pouring tool 102 Pouring part 102a Opening part 121 Tubular main part 122 Liquid repellent member 122a Overhang part 122b Engagement step part 201 Eye drop container 202 Container main body 210 Nozzle (pouring tool)

210a Opening

210b Protruding portion 211 Liquid repellent member RS Rough surface (uneven shape)
sRS Concave and convex shape for auxiliary S1 First surface S2 Second surface

Claims

A liquid repellent member is attached to at least a part of the periphery of the opening through which the content liquid is poured,
At least a part of the periphery of the opening is formed by the liquid repellent member.
The liquid repellent member is made of a non-fluorine resin,
The extraction tool according to claim 1, wherein a fluorine atom is incorporated in a molecular chain of a non-fluorine resin that forms a surface of the liquid repellent member.
The pouring tool according to claim 1 or 2, wherein the surface structure of the liquid repellent member has an uneven shape.
The extraction tool according to claim 3, wherein at least a part of the uneven surface has an auxiliary uneven shape smaller than the uneven shape.
Equipped with a spout part that serves as a spout for the liquid content,
The liquid repellent member is attached to a portion including at least the top surface around which the content liquid passes around the opening provided in the spout portion,
The pouring tool according to any one of claims 1 to 4, wherein at least a part of the top surface side of the pouring port portion is formed by the liquid repellent member.
The spout portion has a cylindrical main portion that rises in a cylindrical shape,
The liquid repellent member has a protruding portion that protrudes outward with respect to the outer peripheral surface of the cylindrical main portion, and is joined to the opening-side edge of the cylindrical main portion at a portion other than the protruding portion. The extraction tool according to claim 5.
The liquid repellent member is formed in an annular shape having an inner diameter that is the same as the inner diameter of the cylindrical main portion, and the inner peripheral surface of the liquid repellent member and the inner peripheral surface of the cylindrical main portion are flush with each other. The extraction tool according to claim 6, wherein an engagement step portion is formed on the inner peripheral surface side of the liquid repellent member so as to engage with an opening side edge portion of the cylindrical main portion.
An opening side edge of the cylindrical main portion is formed in a tapered shape so as to be inclined toward the outer peripheral surface side of the cylindrical main portion, and on the inner peripheral surface side of the liquid repellent member The extraction tool according to claim 7, wherein a tapered curved surface portion that comes into contact with the opening side edge portion of the cylindrical main portion is formed.
The liquid repellent member is attached to the tip side where the opening opens,
The dispensing tool according to any one of claims 1 to 4, wherein the liquid repellent member constitutes at least a part of a tip portion.
The tip surface is
A first surface located on the center side, and a second surface continuous to the outer peripheral side of the first surface,
The extraction tool according to claim 9, wherein the first surface and the second surface are surfaces having different surface free energies.
A protrusion is formed that protrudes along the periphery of the opening,
The liquid repellent member is attached so as to be arranged around the protrusion, and constitutes a part of the tip.
The extraction tool according to claim 10, wherein the tip surface of the protrusion is the first surface, and the surface of the liquid repellent member is the second surface.